JPH069532A - Production of ethylenically unsaturated nitrile - Google Patents

Abstract

PURPOSE: To prepare an ethylenically unsatd. nitrile from an alkene feed stream contg. alkanes having at least two carbon atoms as an impurity.

CONSTITUTION: A preparation method comprises (a) a step to react a hydrocarbon feed stream 2 with an oxygen-contg. gas 4 and ammonia 6 in a reaction zone 4 in the presence of an ammoxidation catalyst to form a gaseous flow 8 contg. ethylenically unsatd. nitriles, alkanes and other gaseous components, (b) a step 12 to recover ethylenically unsatd. nitriles in a nitrile recovering zone B, (c) a step to recover at least part of alkanes from a gaseous flow 14 free from ethylenically unsatd. nitriles, (d) a step D to bring the recovered alkanes 18 into contact with a dehydrogenation catalyst, and (e) a step to recycle 20 the converted alkenes into the reaction zone.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

The present invention relates to a method for producing nitriles, and more particularly to a method for producing ethylenically unsaturated nitriles from a hydrocarbon, an oxygen-containing gas and ammonia in the presence of an ammoxidation catalyst.

Methods for producing nitriles from a suitable hydrocarbon by ammoxidation in the presence of a suitable catalyst are known. For example, the production of acrylonitrile from propylene, ammonia, and air gas feeds is described by Bruce E. Gates et al. (Chemistry of Catalytic Pr
ocessed McGraw-Hill (1979), pages 380-384).

The feed is sent to an ammoxidation reactor where acrylonitrile is produced in the presence of a suitable catalyst, with smaller amounts of other nitrogen containing compounds. The effluent from the ammoxidation reactor is cooled with water to give the desired product in the liquid phase. Gas phase by-products, typically oxygen, carbon dioxide, carbon monoxide, and unreacted hydrocarbons, have been combined with natural gas, eg, Yoshino et al., US Pat. No. 3,591,620. Sent to the boiler for combustion as disclosed in US Pat.

Callahan et al., US Pat. No. 4,33.
No. 5,056 discloses the production of acrylonitrile by catalytic ammoxidation of propylene and the catalytic conversion of propylene in waste gas to acrylonitrile.

Recently, Khoobiar et al., US Pat.
09,502 discloses a recycle process for producing acrylonitrile using propane as a starting material.
Propane is first catalytically dehydrogenated to propylene in the presence of steam. After ammoxidation, the effluent is cooled to recover the desired product, the offgas containing propylene and propane is sent to an oxidation reactor where oxygen selectively reacts with hydrogen to form steam and is removed. The exhaust gas mixture from the selective oxidation reactor contains unreacted propane and propylene, light hydrocarbons and carbon monoxide, which is processed by the separator to remove some of the light hydrocarbons and carbon monoxide from the gas stream. Removed from. The gas stream containing propane and propylene is then recycled to the dehydrogenation reactor. A drawback of the Khoobier et al. Method is that oxygen needs to be removed from the recycle gas as it degrades the dehydrogenation catalyst.

Ramachandran et al., US Pat. No. 4,868,
No. 330 is a recycling process of ammoxidation of propylene with oxygen and ammonia, and after the ammoxidation, the product is recovered by cooling,
The gas stream is compressed and pressure swing adsorption (PS
A) sent to a separator such as a unit to remove carbon oxides and propane and to recycle the residual gas stream containing propylene and propane into a feed stream. In this method, non-reactive propane is introduced into the system as a combustion suppressant. Since commercial grade propylene contains propane as an impurity, it is convenient to select propane as the burn suppressant. The disadvantage of the Ramachandran et al. Method is that propane is non-reactive inside the ammoxidation reactor and it is necessary to remove some of it continuously to prevent accumulation in the system. .

Ramachandran et al., US Pat. No. 4,849,
Nos. 537 and 4,849,538 are processes for the recycle production of nitriles, a process of dehydrogenating propane to propylene, a product gas stream containing a nitrile product by ammonifying propylene with oxygen and ammonia, And carbon oxides and by-products containing unreacted propane, propylene and oxygen, recovering the nitrile from the product gas stream by cooling, some of the carbon oxides by PSA from the nitrile-free gas stream Disclosed is a process comprising the steps of: removing oxygen, removing oxygen from the gas stream, and recycling the resulting propane and propylene-enriched gas stream to a dehydrogenator. In U.S. Pat. No. 4,849,537, a multi-stage reactor is used for propane dehydrogenation, the propylene product is taken from an intermediate stage of the reactor, and unreacted oxygen is passed through the product gas stream passage. Propylene is taken out at a stage downstream from the stage where propylene is taken out. In U.S. Pat. No. 4,849,538, oxygen is removed from the product stream by a selective oxidation reactor located between the PSA unit and the dehydrogenator.

The latter two US patents of Ramachandran et al. Provide a useful procedure for recovering unreacted propane from waste gas in a propane dehydrogenation / ammoxidation plant and avoiding the use of propane as a fuel. . It would be of great benefit to provide an efficient method and system for converting alkanes impure in the hydrocarbon feed stream to an alkene ammoxidation reactor to ethylenically unsaturated nitriles. The present invention makes this possible and allows the use of alkene feed streams containing alkane impurities as feed to the alkene ammoxidation reactor.

The process of the present invention comprises the step of providing a hydrocarbon feed stream containing an alkane and an alkene having at least two carbon atoms, an oxygen-containing gas and ammonia in the gas phase of an ammoxidation reactor. The alkene reacts with oxygen and ammonia in the reactor under the conditions under which the catalyst works effectively to produce the desired ethylenically unsaturated nitriles, but the alkanes present in the feed stream. To provide a method that has virtually no effect on. The product stream from the ammoxidation reactor contains nitrile products, unreacted alkenes, alkanes, oxygen, carbon oxides, nitrogen and argon (if air is used as the oxygen-containing gas), and various other gases. Contains ingredients in small amounts. The product stream from this ammoxidation reactor is sent to a nitrile recovery unit, and nitrile is recovered from the product stream by suitable means. The gaseous effluent from the nitrile recovery unit is then treated by a suitable selective separator to remove at least some of the carbon oxides and other gaseous inert components. The gas stream after removal of these components contains large amounts of unreacted alkenes and alkanes, as well as some carbon oxides and other gaseous components. This gas is introduced into the dehydrogenation reactor and some or all of the alkanes contained in the gas stream are converted to alkenes. The effluent gas from the dehydrogenation reactor is recycled to the ammoxidation reactor.

In a preferred embodiment of the present invention, the alkane is propylene, isobutylene, or a mixture thereof, which produces acrylonitrile, methacrylonitrile, or a mixture thereof, respectively. In another preferred embodiment, the hydrocarbon feed comprises substantially one alkane and one alkene, the alkane and alkene having the same number of carbon atoms and the same isomeric structure. In another preferred embodiment the oxygen containing gas is air. In another preferred embodiment, the catalyst in the ammoxidation reactor is a supported, ammoxidation catalyst comprising bismuth-molybdenum mixed oxide, bismuth-antimony mixed oxide, uranium-molybdenum mixed oxide, iron-antimony. Mixed oxides, and mixtures thereof, where the catalyst in the dehydrogenation reactor is a noble metal such as palladium, platinum, etc. supported on alumina. In another preferred embodiment, the selective separator is a PSA unit and the adsorbent contained therein selectively adsorbs alkanes and alkenes.

The invention further provides a system in which the method according to the invention is implemented. The system is a gas phase ammoxidation reactor having one or more feed inlets and one ammoxidation product outlet, a feed inlet connected to the ammoxidation reactor outlet,
A nitrile recovery unit having a nitrile product outlet, and a waste gas outlet for the remaining components of the first ammoxidation product stream, an inlet connected to the waste gas outlet, a carbon oxide and inert gas removal outlet, Selective separator with outlet for unreacted alkene and alkene-containing stream, and feed inlet connected with outlet for unreacted alkene and alkene-containing stream from selective separation, and ammoxidation reactor It includes a dehydrogenation reactor with a connected outlet.

The hydrocarbon composition used as feed in the process according to the invention generally comprises a major amount of one or more alkenes and a minor amount of one or more alkanes. Alkenes and alkanes, and mixtures of alkenes and alkanes, which are capable of forming the desired ethylenically unsaturated nitriles or mixtures of nitriles under certain conditions can be used, but have 2 to 6, preferably 3 to 4 carbon atoms. Alkenes and alkanes with are preferred. The most preferred alkenes are propylene and isobutylene, and the most preferred alkanes are propane and isobutane. The invention is particularly useful for producing one unsaturated nitrile from a hydrocarbon feed containing alkenes and alkanes having the same isomeric structure with the same number of carbon atoms. For example, when acrylonitrile is produced, the hydrocarbon feed mixture preferably comprises substantially propylene and propane, and when methacrylonitrile is produced it preferably comprises substantially isobutylene and isobutane. Commercial grade propylene and isobutylene contain small amounts of propane and isobutane, respectively, as impurities, which is the preferred hydrocarbon feed source. This is because these gases are cheaper than pure propylene or isobutylene. The hydrocarbon mixture used in the reaction depends, of course, on the nitrile produced.
The process according to the invention is described by taking as an example the production of acrylonitrile from propylene and propane, but this does not impose any limitation on the scope of the invention.

The amount of alkane contained in the hydrocarbon feed containing the alkene as the main amount is not critical. But,
An alkene content of at least about 80% by volume in the feed mixture is preferred for efficient practice of the invention. In a preferred embodiment, the alkene is included in the feed mixture at least about 90% by volume, and in the most preferred embodiment, the alkene is included in the feed mixture at least about 95% by volume.

The oxygen-containing gas used in the present invention is air, oxygen-enriched air, another oxygen-inert gas mixture or substantially pure oxygen. Oxygen-enriched air is air that contains more oxygen than is originally contained in the air. Oxygen-inert gas mixtures include oxygen-nitrogen mixtures, oxygen-carbon dioxide mixtures and the like. Air and oxygen-enriched air are the preferred oxygen sources. This is because they are cheaper than high-purity oxygen, and nitrogen contained in the gas acts as a combustion inhibitor.

According to one embodiment of the process according to the invention, a hydrocarbon mixture containing the desired alkenes and alkanes or a mixture of alkenes and alkanes in the gas phase, oxygen-containing gas and ammonia, alkenes with oxygen and In a reactor having a catalyst that is amoxidized with ammonia, but does not substantially affect the alkane,
With the desired olefinically unsaturated nitrile as the main product,
Carbon monoxide and carbon dioxide as by-products, as well as unreacted alkenes and oxygen, alkanes contained in the hydrocarbon feed, and various other components such as nitrogen and argon (air or oxygen-enriched air as the oxygen source. And when used as a) and a condition that forms a gaseous product stream containing a small amount of water vapor. Following the ammoxidation reaction, unsaturated nitriles are recovered from the gaseous product stream by a nitrile product recovery unit. The nitrile-free gas stream is then sent to a separator where some of the carbon oxides, nitrogen and, if present, argon, and some of the other light components, prevent their build up in the system. To be removed. After removal of these components, the gas component contains unreacted alkenes and the balance of alkanes, carbon oxides, nitrogen, etc., but the gas contains catalytic reagents capable of dehydrogenating some or all of the alkanes contained to the corresponding alkenes. Sent to the gas phase reactor. The effluent from the dehydrogenation reactor is recycled to the alkene ammoxidation reactor to convert the newly produced alkene to unsaturated nitrile.

The present invention will be better understood with reference to the accompanying figures. It should be noted that auxiliary devices such as compressors, heat exchangers, valves, etc., which are not necessary for understanding the invention, are not shown.

Referring to the figure, the system according to the invention comprises an alkene ammoxidation reactor A, an unsaturated nitrile recovery unit B, a hydrocarbon separator C and a dehydrogenation reactor D.

Reactor A can be any reactor suitable for ammoxidation, but is typically a fixed, movable, fluid, slurry or moving catalyst bed. In reactor A,
A heat exchanger (not shown) for removing heat generated by the reaction, which is an exothermic reaction, can be provided. Details of typical designs of preferred reactors are already known,
It is not a feature of the invention.

Reactor A has a catalyst capable of producing ethylenically unsaturated nitriles from alkenes with high selectivity. All known catalysts for the oxidation of alkenes to nitriles under the specified conditions can be used in the process according to the invention. Suitable catalysts that can be used in the first ammoxidation reactor include oxide mixtures of bismuth and molybdenum, iron and antimony, bismuth and antimony, uranium and antimony and the like. Other suitable catalysts are described in Gate et al., Chemistry of Catalitic Processes, M.
cGraw Hill (1979), pages 349-350, and Yoshino et al., US Pat. No. 3,591,620. Both of the above are referenced as part of this specification. These catalysts may be precipitated on silica and their use is known to those skilled in the production of nitriles. The type of alkene ammoxidation catalyst used in the process of this invention is not a critical part of this invention. Reactor A
Although the catalyst used in, is capable of converting a small amount of alkanes contained in the hydrocarbon feed to unsaturated nitriles,
This conversion is incidental only and the use of this catalyst for such purpose is not intended.

On the inlet side of the alkene ammoxidation reactor A, a new hydrocarbon feed pipe 2, a feed pipe 4 for oxygen-containing components, and an ammonia feed pipe 6 are provided. If desired, the reactants can be combined and introduced into reactor A by a single line, as described below. The product take-out side of the reactor A is connected to an unsaturated nitrile recovery unit via a nitrile recovery unit supply pipe 8.

The nitrile recovery unit B may be any suitable device for recovering unsaturated nitriles from a gas stream, such as a condenser or a liquid gas scrubber. When the nitrile recovery unit B is a gas scrubber, that is, an absorber, it is usually a packed bed and the pipe 10 is installed. Water or an aqueous or non-aqueous liquid is supplied via this line to unit B and is contacted with the product gas stream introduced from reactor A into this unit. Unit B has a nitrile product recovery pipe 1
2 is also provided. The unit B is connected to the separator C via the gaseous substance outflow pipe 14.

The main purpose of the separator C is to prevent the build-up of carbon dioxide, carbon monoxide, nitrogen and other produced by-product gases and the inert gases introduced into the system in the system. . This unit may be any unit that can achieve the purpose. The separator C is usually an adsorber, a desorber or a membrane separation unit, and one or a plurality of separators in series can be used. In a preferred embodiment of the invention, the separator C is a pressure swing adsorption (PSA) unit or a temperature swing adsorption (TSA) unit. The most preferred embodiment is a pressure swing adsorption (PSA) unit.

PSA is a known means for separating specific components of a gas mixture by varying the degree of adsorption to a particulate adsorbent retained in a stationary bed. Typically, two or more beds as described above are operated in a cycle where the adsorption step under relatively high pressure and the desorption or bed regeneration step under relatively low pressure or reduced pressure are cycled. is there. The desired ingredients can be obtained at any stage of these processes. The above cycle is
In addition to the basic steps of adsorption and regeneration, other steps can be included. It is also common to operate two or more beds 180 degrees out of phase to ensure false continuous production of the desired product. The adsorption step of the PSA cycle is generally carried out under pressure, but it can also be carried out under atmospheric pressure, in which case the desorption step is carried out under reduced pressure. This is because the essence for operating the system is the pressure difference between the adsorption and desorption steps.

When the separator C is a PSA unit, the adsorbent contained therein may be any adsorbent having a substantially larger adsorption capacity for alkenes and alkanes than carbon oxide, nitrogen and argon. It may be one. By selecting the appropriate adsorbent, the operation of the PSA unit can be easily controlled by known operating means, and the recycle stream formed is substantially the major amount of alkenes and alkanes and small amounts of carbon oxides, nitrogen and other Of inert gas. Silica gel and zeolite molecular sieves are the preferred adsorbent materials, most preferably silica gel.

The separator C is provided with a waste gas exhaust pipe 16 and a recycle pipe 18, the latter of which is connected to the ammoxidation reactor D.

Dehydrogenation reactor D may be any reactor suitable for dehydrogenating alkanes to alkenes. Details of suitable reactor designs are known and such reactor designs are not a feature of the invention. Reactor D may be a small scale dehydrogenation unit because the amount of alkane introduced into reactor A in the hydrocarbon stream is generally small. A typical dehydrogenation reactor is described in the aforementioned US Pat. No. 4,609,
502, 4,849,537, and 4,849,53
No. 8, the disclosures of which are incorporated by reference as part of the present invention.

According to one embodiment of the invention, the reactor D may comprise a pair of units arranged in parallel and operated in different phases, one in the production process and the other in the regeneration process. When the efficiency of the reactor in the manufacturing process falls to a predetermined level, the regenerated reactor is put in the manufacturing process, and the reactor in the manufacturing process is put in the regeneration process.

The catalyst used in the reactor may be any catalyst as long as it can dehydrogenate an alkane under the reaction conditions of the reactor D. Typical catalysts and reaction conditions are described in the aforementioned U.S. Pat. No. 4,609,502,4,84.
9,537, and 4,849,538. Suitable catalysts are supported and unsupported Group VIII noble metals, such as platinum on an alumina support, with or without a promoter. As with the reactor D design, the type of dehydrogenation catalyst used is not a feature of the invention.

In the embodiment shown in the figure, the reactor D is provided with a product withdrawal pipe 20, which is connected to the hydrocarbon feed pipe 2.

In the illustrated embodiment, a hydrocarbon feed stream containing the desired alkenes and alkanes is introduced into reactor A via inlet line 2. At the same time, the oxygen-containing gas stream and the ammonia gas are introduced into reactor A via lines 4 and 6, respectively. As a variation of the arrangement, hydrocarbon, oxygen-containing gas and ammonia gas are brought together,
It is also possible to introduce the gas mixture into the reactor A via a single pipe. The arrangement of inlets used is selectable and depends on the type of reactor used to carry out the invention.
In fixed bed reactors, the feed components are often mixed before being introduced into the reactor and introduced into the reactor via a single pipe. On the other hand, in fluidized bed reactors, the feed components are often introduced separately into the reactor.

The feed gas introduced into reactor A contacts the catalyst and reacts to produce the desired ethylenically unsaturated nitriles. The conditions for hydrocarbon ammoxidation are known and are not a feature of the present invention. Typically, the ammoxidation reaction is carried out at an elevated temperature, typically about 250 to 600 ° C., usually about 300 to 500 ° C., low pressure,
Typically about 2 to 50 psig, usually about 3 to 30 p
It is done in sig. The reactants generally pass through the reactor at a rate of about 0.5 to 5 feet / second. The ratio of oxygen to hydrocarbons and the typical ratio of ammonia to hydrocarbons in the feed stream are each about 0.
3: 1 to 10: 1, and about 0.8: 1 to 1.3:
It is 1.

The amount of unreacted alkene present in the effluent gas from reactor A depends in part on the conversion per pass of alkene introduced into the ammoxidation reactor.
One of ordinary skill in the art will be able to tailor the ammoxidation reactor to the desired conversion of alkenes by adjusting the choice of catalyst, operating pressure, and the like. At low conversions, ie at 60% conversion, a large amount of unreacted alkene will remain in reactor A. For example,
When pure oxygen is introduced into the ammoxidation reactor,
It is estimated that about 10 to 15% of unreacted alkene is contained in the effluent stream from Reactor A when operating at 80% conversion in the process according to the invention, but at 60% conversion. If so, more unreacted alkene will be included.

The product stream exiting reactor A contains nitrile as a major component and carbon dioxide and carbon monoxide as by-products. As mentioned above, the product stream generally contains unreacted alkenes, oxygen, alkanes that did not undergo the desired reaction inside Reactor A, small amounts of other by-products, impurity gases, and non-reactive gases such as It also includes saturated hydrocarbons such as nitrogen, argon and methane. The product gas stream exits reactor A via line 8 and is preferably cooled to about 30 to 200 ° C through a heat exchanger (not shown). The cooled product gas stream is introduced into the nitrile recovery means B and the nitrile product is recovered from the gas stream.
When scrubbing is used as the means for recovery, water can be used as a solvent, which solvent dissolves substantially all of the nitrile in the product gas and the solution containing the nitrile from scrubber B via line 12. Is discharged.
It is usually further processed to recover the substantially pure nitrile. The scrubbed gas stream is discharged from the nitrile recovery means B through the pipe 14 and introduced into the separator C.

As mentioned above, separator C serves to prevent the build up of carbon dioxide, carbon monoxide, nitrogen and other produced by-product gases, and inert gases into the system. It is desirable to remove carbon oxides and inert gases (nitrogen and argon) in excess of what is required to maintain a non-combustible atmosphere in the system, which makes the system more efficient. . To this end, in each pass an amount of carbon oxide equal to the amount of by-products produced in reactor A, and an amount of inert gas equal to the amount introduced into the reactor A by the feed stream. It is necessary to remove gases (nitrogen, argon, non-reactive hydrocarbons, etc.).

Separator C can be operated at ambient pressure, and in some cases it is preferably operated under pressure. This is especially the case when separator C is a PSA unit. If separator C is operated at elevated pressure, the effluent gas stream from nitrile recovery unit B may be passed through a compressor or other suitable means (not shown) to increase the pressure to the desired operating pressure. . PSA units typically operate in the pressure range of about 3 to 50 psig, preferably about 20 to 40 psig. The preferred operating pressure range depends on the type of adsorbent used.

Part of the nitrogen and carbon oxide and all or part of the oxygen introduced into the separator C via the pipe 14 are exhausted from the system via the pipe 16. These exhaust gases are preferably combusted and / or released to the atmosphere.
If desired, oxygen can be recovered from the exhaust stream and recycled to the feed stream to the reactor to increase the operating capacity of the system. Gas not evacuated from the system via line 16 is sent to reactor D via line 18 to dehydrogenate some or all of the alkanes contained in the incoming gas stream to the corresponding alkenes.

The alkane contained in the gas stream sent to the reactor D through the pipe 18 is brought into contact with the catalyst contained in the reactor under appropriate conditions to be dehydrogenated. The alkane dehydrogenation reaction is typically described in the aforementioned US Pat.
9,502, 4,849,537, and 4,849,
As disclosed in US Pat. No. 538, about 400 to 700.
It is carried out in a temperature range of 0 ° C. and a pressure range of about 0.1 to 5 bar. The dehydrogenation reaction is generally an endothermic reaction, and it is preferable to provide a means for heating the reactant stream in the reactor or a means (not shown) for heating the contents of the reactor. The dehydrogenation reaction can be operated with low efficiency. This is because if the amount of alkane equal to the amount supplied to the system via the hydrocarbon supply pipe 2 can be converted in one pass, the system can be balanced.

The oxygen contained in the feed stream to reactor D is
The activity of the dehydrogenation catalyst contained in the reactor D is reduced. Since it is not necessary to operate reactor D with high efficiency, the reduction in the activity of the dehydrogenation catalyst can be reduced to some extent by removing the oxygen in the gas stream introduced into reactor D. This can be achieved by removing the oxygen in the separator C, for example by using equipment such as a multi-sorbent bed, one of which is capable of separating oxygen from the hydrocarbons to be recycled. . Alternatively, the oxygen is removed by reacting with the hydrogen present in the gas stream by passing the gas stream through a selective oxidation reactor of the type shown in US Pat. No. 4,849,538 mentioned above. You can also do it.

However, it is not necessary to remove oxygen from the feed stream to reactor D. This is because it is not necessary to operate the reactor D with high efficiency.
Further, as disclosed in the above-mentioned US Pat. No. 4,849,537, the catalyst can be easily regenerated by heating and burning the accumulated carbon.

It is desirable to introduce hydrogen into reactor D to prolong the life of the catalysts involved, especially if oxygen is not removed from the gas stream before it is introduced into reactor D. This is simply accomplished by recycling some or all of the hydrogen to the recycled stream while passing the previous pass of the gas stream through the dehydrogenation reactor.

The product gas flow from the reactor D passes through the pipe 20 and is recycled to the reactor A. The effluent from reactor D may be sent directly to reactor A, or it may be mixed with fresh hydrogen introduced into the system via line 2 as shown in the figure.

Known devices can be used to monitor and automatically regulate the gas flow in the system for automatic continuous operation in an efficient manner.

The method of the invention results in a substantially reduced flammability, together with its simplicity, ease of operation, low initial investment, low operating costs. The process of the present invention can be operated at a relatively low conversion of feed hydrocarbons to the desired product, resulting in substantially improved selectivity to the desired nitrile product. Selectivity refers to the amount of desired product divided by the total product. Using cheaper feedstocks, such as commercial grade propylene or isobutene, run the system at relatively low conversions to obtain greater selectivity, thereby achieving higher yields for the desired product. There are enormous advantages to doing.

The present invention is described in further detail below, but parts, percentages, and ratios are by volume unless otherwise noted.

Example A gas phase acrylonitrile was produced in the same reaction system as in FIG. Reactor A is a gas phase fluidized bed reactor,
Silica supported iron-antimony oxide mixture is packed, Reactor D is a gas phase fixed bed reactor, alumina supported platinum is packed, Reactor C is silica gel packed pressure swing adsorption. It is a device. The hydrocarbon feed to the system consisted of 93% by volume propylene and 7% by volume propane. The feed to Reactor A contained fresh feed components and recycled system components. The flow rate and composition at various points are shown in the table.

The conversion of propylene and the selectivity to acrylonitrile in reactor A were 96% and 78%, respectively. The conversion of propane and the selectivity to propylene in the dehydrogenation reactor D were 40% and 93%, respectively.

The examples show that the process according to the invention is useful for converting a feed containing a mixture of alkanes and alkenes to ethylenically unsaturated nitriles. Although the present invention has been described based on the embodiments, it is merely an example, and various changes are included in the present invention. For example, the reaction can be carried out under conditions suitable for producing other nitriles. Similarly, other catalysts, adsorbents, and other gas separation means can be used.
It can also be carried out with device arrangements other than those shown.

[Brief description of drawings]

FIG. 1 is a block diagram showing an example of a system for producing ethylenically unsaturated nitriles according to the present invention.

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Claims (16)

[Claims] 1. A method for producing ethylenically unsaturated nitriles from an alkene feed stream containing an alkane as an impurity having at least two carbon atoms, comprising: (a)
The feed stream is catalyzed with an oxygen-containing gas and ammonia in a reaction zone in the presence of an ammoxidation catalyst for the reaction of the alkene, oxygen, and ammonia to form ethylenically unsaturated nitriles. Reacting under conditions such that they develop, thereby producing a gas stream containing ethylenically unsaturated nitriles, alkanes, and other gas components, (b) the ethylenically unsaturated nitriles from said gas stream, Recovering in a nitrile recovery zone, (c) recovering at least a portion of the alkane from the gas stream containing substantially no ethylenically unsaturated nitriles, (d) recovered alkane and dehydrogenation catalyst Contacting and under conditions such that at least some of said alkanes are converted to the corresponding alkenes. And a step of recycling (e) the conversion alkene to said reaction zone,
The above method comprising: 2. The method according to claim 1, wherein the oxygen-containing gas is selected from the group consisting of pure oxygen, air and a gas richer in oxygen than air. 3. The method of claim 2 wherein the alkene is selected from the group consisting of propylene, isobutylene, and mixtures thereof and the alkane is selected from the group consisting of propane, isobutane, and mixtures thereof. 4. The method of claim 3 wherein the alkene is propylene and the alkane is propane. 5. The method of claim 3 wherein the alkene is isobutylene and the alkane is isobutane. 6. The ammoxidation catalyst is selected from the group consisting of bismuth-molybdenum mixed oxide, bismuth-antimony mixed oxide, uranium-molybdenum mixed oxide, iron-antimony mixed oxide, and mixtures thereof. The method of claim 1, wherein: 7. The method of claim 1, wherein the dehydrogenation catalyst is one or more Group VIII noble metals. 8. The method of claim 1, wherein step (c) is performed by pressure swing adsorption. 9. The method of claim 8 wherein the pressure swing adsorption is performed using silica gel or zeolite molecular sieves. 10. The method of claim 1, wherein the nitrile recovery zone comprises a liquid scrubber. 11. A system for producing ethylenically unsaturated nitriles from a hydrocarbon stream containing a mixture of alkanes and alkenes, comprising: (a) supplying said hydrocarbon stream, oxygen and ammonia, Gas-phase alkene ammoxidation reactor in which the alkene in the hydrogen stream is converted to ethylenically unsaturated nitriles and then the first product stream containing ethylenically unsaturated nitriles, carbon dioxide, and alkanes is vented Means, (b) an ethylenically unsaturated nitriles recovery means for supplying the first product stream and producing an ethylenically unsaturated nitrile product and a nitrile-free stream containing carbon dioxide and alkanes;
(C) a separation means that is fed with the nitrile-free stream to produce an exhaust stream containing carbon dioxide and a recycle stream containing alkanes; and (d) the recycle stream is fed to alkene alkanes in the recycle stream. A gas phase alkane dehydrogenation reactor means for converting the alkene-containing product stream to an exhaust stream and tubing means for transferring the alkene-containing product stream to the alkene ammoxidation reactor means. 12. The alkene ammoxidation reactor is selected from the group consisting of bismuth-molybdenum mixed oxide, bismuth-antimony mixed oxide, uranium-molybdenum mixed oxide, iron-antimony mixed oxide, and mixtures thereof. The system of claim 11 having a catalyst. 13. The system of claim 12, wherein the alkane dehydrogenation reactor has a catalyst selected from Group VIII noble metals. 14. The system of claim 11, wherein said separating means is a pressure swing adsorption unit. 15. The system of claim 14, wherein the pressure swing adsorption unit comprises an adsorbent selected from silica gel, zeolites, and mixtures thereof. 16. The system according to claim 11, wherein the means for recovering ethylenically unsaturated nitriles is a liquid scrubber.